WO2021222709A1 - Membrane à température d'arrêt réduite et composition polymère pour sa fabrication - Google Patents

Membrane à température d'arrêt réduite et composition polymère pour sa fabrication Download PDF

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Publication number
WO2021222709A1
WO2021222709A1 PCT/US2021/030095 US2021030095W WO2021222709A1 WO 2021222709 A1 WO2021222709 A1 WO 2021222709A1 US 2021030095 W US2021030095 W US 2021030095W WO 2021222709 A1 WO2021222709 A1 WO 2021222709A1
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WIPO (PCT)
Prior art keywords
density polyethylene
shutdown
polymer composition
polymer
reducing additive
Prior art date
Application number
PCT/US2021/030095
Other languages
English (en)
Inventor
Christian Ohm
Kirsten Markgraf
Original Assignee
Celanese International Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Celanese International Corporation filed Critical Celanese International Corporation
Priority to EP21797222.3A priority Critical patent/EP4143139A4/fr
Priority to CN202180047330.4A priority patent/CN115803291A/zh
Priority to JP2022566638A priority patent/JP2023524104A/ja
Priority to MX2022013577A priority patent/MX2022013577A/es
Priority to BR112022022254A priority patent/BR112022022254A2/pt
Priority to KR1020227042121A priority patent/KR20230005958A/ko
Publication of WO2021222709A1 publication Critical patent/WO2021222709A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/0633—LDPE, i.e. low density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0038—Plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • C—CHEMISTRY; METALLURGY
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J2423/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Definitions

  • Polyethylene polymers have numerous and diverse uses and applications.
  • high density polyethylenes are valuable engineering plastics, with a unique combination of abrasion resistance, surface lubricity, chemical resistance and impact strength. They find application in the production of high strength fibers for use in ropes and anti-ballistic shaped articles and in the production of other elongated articles, such as membranes for electronic devices.
  • processing by conventional techniques, such as melt extrusion is not always possible.
  • One alternative method for producing fibers and other elongated components from polyethylene polymers is by gel-processing in which the polymer is combined with a solvent.
  • the resultant gel is extruded into a fiber or membrane, and may be stretched in one or two directions. Also, part or all of the solvent may be removed from the product.
  • Membranes made from polyethylene polymers through gel-processing can be formed to have many beneficial properties.
  • the membranes can be formed with micro-pores.
  • Microporous polyethylene membranes formed through gel-processing are particularly well suited for use as a separator in a battery, such as a lithium ion battery.
  • the microporous membrane for instance, can separate an anode from a cathode and prevent a short circuit between the active battery components.
  • the microporous membrane permits ions to pass through due to the porous nature of the material.
  • the ion permeability characteristics of the microporous polyethylene membrane makes the material particularly well suited for regulating electrochemical reactions within the battery.
  • the polyethylene membranes In addition to the microporous nature of the polyethylene membrane and to possessing beneficial strength and other physical properties, the polyethylene membranes also offer what is referred to in the art as having an effective “shutdown effect”.
  • the shutdown effect refers to the self-closing of micro-pores within the polyethylene separator when it surpasses a certain temperature. When the pores in the polyethylene membrane are closed upon reaching a certain temperature, ions can no longer pass through the membrane and the electrochemical function of the battery stops. This effect becomes an important safety feature for the battery as it prevents thermal runaway reactions from continuing and prevents the battery from overheating and creating a potentially hazardous situation.
  • the present disclosure is directed to polyolefin compositions well suited for gel-processing applications. More particularly, the present disclosure is directed to a polymer composition containing a high density polyethylene polymer well suited for producing microporous, ion permeable membranes that may be used as separators in batteries.
  • the polymer composition is formulated so as to have a lower shutdown temperature so that the membrane becomes substantially impermeable once the membrane is subjected to higher temperatures in a particular environment. For instance, when used as a battery separator, the shutdown temperature of the membrane can prevent the battery from a thermal runaway condition.
  • the present disclosure is directed to a polymer composition for producing gel extruded articles.
  • the polymer composition comprises a plasticizer, high density polyethylene particles and a shutdown reducing additive.
  • the shutdown reducing additive comprises particles that are combined with the high density polyethylene particles and the plasticizer.
  • the shutdown reducing additive reduces the shutdown temperature such that the shutdown temperature is at least about 1 4°C lower, such as at least about 1 8°C lower, such as at least about 2.2°C lower, such as at least about 2.5°C lower than a polymer composition where the shutdown reducing additive is replaced by further amounts of the polyethylene particles.
  • the shutdown reducing additive reduces the shutdown temperature of the polymer composition by greater than about 3°C, such as by greater than about 4°C, such as greater than about 5°C, such as greater than about 6°C, such as greater than about 7°C.
  • the shutdown reducing temperature of the polymer composition is generally reduced by no more than about 20°C, such as by no more than about 15°C, such as by no more than about 10°C.
  • the shutdown reducing additive may comprise a different high density polyethylene in relation to the primary high density polyethylene particles present in the composition, a low density polyethylene, a linear low density polyethylene, a metallocene catalyzed linear low density polyethylene, a polyethylene wax, a hydrogenated fatty acid, an amide of a fatty acid, a middle density polyethylene, a dimer of a fatty acid, a plastomer, an elastomer, or mixtures thereof.
  • the shutdown reducing additive is a polyethylene polymer having a melt flow rate of from about 0.01 g/10 min to about 70 g/10 min, such as from about 0.05 g/10 min to about 50 g/10 min, such as from about 0.1 g/10 min to about 30 g/10 min, such as from about 1 g/10 min to about 20 g/10 min.
  • the shutdown reducing additive can be present in the polymer composition in an amount from about 10% to about 40% by weight, such as in an amount from about 15% to about 35% by weight, such as in an amount from about 20% to about 30% by weight.
  • the high density polyethylene particles can, in one embodiment, have a median particle size by volume of less than about 150 microns, such as less than about 125 microns, and generally greater than about 50 microns.
  • the shutdown reducing additive can be in the form of particles having a median particle size by volume of less than about 800 microns, such as less than about 600 microns, such as less than about 400 microns, such as less than about 200 microns, and generally greater than about 25 microns, such as greater than about 50 microns.
  • the polymer composition contains the high density polyethylene resin in an amount up to about 50% by weight, such as from about 0.5% to about 15% by weight, such as from about 2% to about 8% by weight.
  • the plasticizer for instance, can be present in the composition in an amount greater than about 50% by weight, such as in an amount greater than about 60% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount less than about 90% by weight.
  • the plasticizer may comprise a mineral oil, a paraffinic oil, a hydrocarbon oil, an alcohol, or the like.
  • the plasticizer may comprise decaline, xylene, dioctyl phthalate, dibutyl phthalate, stearyl alcohol, oleyl alcohol, decyl alcohol, nonyl alcohol, diphenyl ether, n-decane, n-dodecane, or mixtures thereof.
  • the plasticizer may comprise a C5-C12 hydrocarbon, such as a C5-C12 saturated hydrocarbon.
  • the plasticizer may comprise heptane, hexane, a paraffin, or the like.
  • the high density polyethylene used to produce the particles can have a relatively high molecular weight.
  • the use of higher molecular weight polyethylene particles may be beneficial, especially in applications where greater strength properties are needed or desired.
  • the polyethylene used to produce the particles can have a molecular weight of greater than about 500,000 g/mol, such as greater than about 700,000 g/mol, such as greater than about 1 ,000,000 g/mol, such as greater than about 1 ,500,000 g/mol, and less than about 4,000,000 g/mol, such as less than about 3,500,000 g/mol.
  • the polyethylene used to produce the particles comprises a Ziegler- Natta catalyzed high molecular weight polyethylene.
  • the present disclosure is also directed to polymer articles formed from the above polymer composition.
  • the polymer articles can be produced through a gel extrusion or gel-spinning process.
  • Polymer articles made in accordance with the present disclosure include fibers, films, such as membranes, or the like.
  • a significant portion of the plasticizer is removed. For example, in one aspect, greater than 95% by weight, such as greater than about 98% by weight of the plasticizer is removed in forming the polymer article. Consequently, polymer articles made in accordance with the present disclosure generally contain the high density polyethylene combined with the shutdown reducing additive.
  • the resulting polymer article can contain the high density polyethylene polymer in an amount from about 60% to about 98% by weight, such as in an amount from about 65% by weight to about 97% by weight.
  • the shutdown reducing additive can be present in the polymer article in an amount from about 2% by weight to about 40% by weight, such as from about 3% by weight to about 35% by weight, such as in an amount from about 4% to about 10% by weight.
  • the present disclosure is also directed to a process for producing polymer articles.
  • the process includes the steps of forming a gel-like composition from the polymer composition described above.
  • the gel-like composition is then extruded through a die to form a polymer article.
  • the polymer article for instance, may comprise fibers, a continuous film, or a discontinuous film, such as a porous membrane.
  • at least part of the plasticizer is separated and removed from the polyethylene article. For instance, in one embodiment, greater than 80%, such as greater than 90%, such as greater than 95%, such as greater than 98% of the plasticizer is removed during formation of the polymer article.
  • an extraction solvent such as dichloromethane is combined with the polymer composition before or during formation of the polymer article.
  • the extraction solvent can be used to facilitate removal of the plasticizer.
  • Fig. 1 is a plot or graph illustrating the shutdown temperature of a microporous membrane using an Impedance Test
  • FIG. 2 is a cross-sectional view of an electronic device, such as a battery, incorporating a porous membrane made in accordance with the present disclosure.
  • the shutdown temperature of a polymer article can vary depending upon the type of test and instrument used to measure the shutdown temperature.
  • the shutdown temperature can vary widely depending upon the procedure, molecular weight of the base resin, and equipment used to make the determination.
  • any reported shutdown temperatures for various products can be much lower than if a different test or technique is used.
  • the shutdown temperature of a polymer article can be determined according to the “Impedance Test,” the “Thermomechanical Analysis Test,” and the “Differential Scanning Calorimetry Test.
  • the Impedance Test is the only test that directly measures shutdown temperature. The following tests are defined as follows.
  • the impedance spectroscopy test setup consists of a glass measurement cell containing two steel electrodes. According to the impedance spectroscopy method, the sample is soaked in an electrolyte (1 M LiPF6 in 1 :1 ethylene carbonate/dimethyl carbonate) and assembled into the cell between the electrodes. The measurement cell is then connected to an impedance spectrometer that records impedance spectrum every 50 seconds at a frequency between 100Hz and 100kHz. The measurement cell is then placed in an oven and heated over 2 hours from 110°C to 150°C while continuously recording impedance spectra. Data evaluation is done with a plot of impedance versus temperature and shutdown temperature is indicated by midway of a steep increase in impedance.
  • FIG. 1 An example plot is demonstrated in which the arrows indicate shutdown temperature.
  • the test can be conducted using an HCP-803 potentiostat available from Biologic Science Instruments.
  • the dynamic strain is measured while the sample is subjected to a temperature regime and a static force of 0.2N with a force multiplier of 0.5.
  • the test is performed over a temperature range from room temperature (25-30°C) to 160°C with a heating rate of 2°C/min.
  • the frequency is set at 0.1 Hz.
  • Data evaluation is done with a plot of dynamic strain versus temperature and the softening point is indicated by the dynamic strain inflection point.
  • the test can be conducted on a Perkin Elmer DMA 8000 dynamic mechanical analyzer.
  • the melting point of the sample can be determined by ISO Test No. 11357 under the following conditions: The sample is heated from 0°C to 180°C with a heating rate of 10°C/min and held isothermally for 5 min at 180°C. After the isothermal hold, the sample is cooled to 0°C with a heating rate of 10°C/min. Finally, the sample is heated to 180°C with a heating rate of 20°C. The sample is inerted with nitrogen during all steps of the DSC procedure. The test can be conducted using a DSC Q2000 calorimeter available from TA Instruments.
  • puncture strength is measured according to ASTM Test D3763 and measures the ability of a membrane to withstand a foreign particle from causing a hole or defect.
  • the test is conducted on a testing device, such as an I nstron CEAST 9340 device.
  • the drop height is 0.03 to 1.10 m.
  • the impact velocity is 0.77 to 4.65 m/s.
  • the maximum dropping mass is 37.5 kg and the maximum potential energy is 405 J. Puncture strength is measured in slow speed puncture mode at 1.67 mm/s.
  • melt flow rate of a polymer or polymer composition is measured according to ISO T est 1133 at 190°C and at a load of 2.16 kg (unless otherwise indicated).
  • the density of a polymer is measured according to ISO Test 1183 in units of g/cm 3 .
  • Average particle size (d50) is measured using laser diffraction/light scattering, such as a suitable Horiba light scattering device.
  • Guriev permeability can be measured according to the Gurley Test, using a Gurley permeability tester, such as Gurley Densometer, Model KRK 2060c commercially available from Kumagai Riki Kogyo Co., LTD. The test is conducted according to ISO Test 5636. The Gurley Test measures air permeability as a function of the time required for a specified amount of air to pass through a specified area under a specified pressure. The units are reported in sec/100 ml. [00038] Porosity (%) is measured according to the following procedure.
  • Dfilm density of specimen
  • mg/mm3 Wt weight of specimen
  • mg THK thickness of specimen
  • mm Square area of specimen
  • Dpolymer Density(polymer) 0.95 (g/cm3)
  • the present disclosure is directed to a polymer composition well suited for producing gel extruded articles, such as fibers and films, including porous membranes.
  • the polymer composition contains a polyethylene resin, such as high density polyethylene particles, combined with a plasticizer and a shutdown reducing additive.
  • the shutdown reducing additive comprises particles that are combined with the high density polyethylene particles and, when the composition is formed into a porous membrane, reduces the shutdown temperature of the membrane.
  • the shutdown reducing additive can be incorporated into the polymer composition in relatively great amounts without comprising the physical or mechanical properties of articles made from the composition.
  • a shutdown reducing additive can be incorporated into the polymer composition of the present disclosure without substantially effecting the mechanical properties of a membrane made from the composition.
  • any suitable high density polyethylene polymer may be used to form the primary polymer component and the matrix polymer of the polymer composition.
  • the high density polyethylene has a density of about 0.93 g/cm 3 or greater, such as about 0.94 g/cm 3 or greater, such as about 0.95 g/cm 3 or greater, and generally less than about 1 g/cm 3 .
  • the high density polyethylene polymer can be made from over 90% ethylene derived units, such as greater than 95% ethylene derived units, or from 100% ethylene derived units.
  • the polyethylene can be a homopolymer or a copolymer, including a terpolymer, having other monomeric units.
  • the high density polyethylene can be a high molecular weight polyethylene, a very high molecular weight polyethylene, and/or an ultrahigh molecular weight polyethylene.
  • “High molecular weight polyethylene” refers to polyethylene compositions with an average molecular weight of at least about 3x10 5 g/mol and, as used herein, is intended to include very-high molecular weight polyethylene and ultra-high molecular weight polyethylene.
  • the molecular weights referenced herein are determined in accordance with the Margolies equation ("Margolies molecular weight").
  • Very-high molecular weight polyethylene refers to polyethylene compositions with a weight average molecular weight of less than about 3x10 6 g/mol and more than about 1x10 6 g/mol. In some embodiments, the molecular weight of the very-high molecular weight polyethylene composition is between about 2x10 6 g/mol and less than about 3x10 6 g/mol.
  • Ultra-high molecular weight polyethylene refers to polyethylene compositions with an average molecular weight of at least about 3x10 6 g/mol.
  • the molecular weight of the ultra-high molecular weight polyethylene composition is between about 3x10 6 g/mol and about 30x10 6 g/mol, or between about 3x10 6 g/mol and about 20x10 6 g/mol, or between about 3x10 6 g/mol and about 10x10 6 g/mol, or between about 3x10 6 g/mol and about 6x10 6 g/mol.
  • the high density polyethylene is a homopolymer of ethylene.
  • the high density polyethylene may be a copolymer.
  • the high density polyethylene may be a copolymer of ethylene and another olefin containing from 3 to 16 carbon atoms, such as from 3 to 10 carbon atoms, such as from 3 to 8 carbon atoms.
  • these other olefins include, but are not limited to, propylene, 1 -butene, 1-pentene, 1 -hexene, 1- heptene, 1-octene, 4-methylpent-1-ene, 1-decene, 1-dodecene, 1-hexadecene and the like.
  • polyene comonomers such as 1 ,3- hexadiene, 1 ,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1- ene, 1 ,5-cyclooctadiene, 5-vinylidene-2-norbornene and 5-vinyl-2-norbornene.
  • the amount of the non-ethylene monomer(s) in the copolymer may be less than about 10 mol. %, such as less than about 5 mol. %, such as less than about 2.5 mol. %, such as less than about 1 mol. %, wherein the mol. % is based on the total moles of monomer in the polymer.
  • the high density polyethylene may have a monomodal molecular weight distribution.
  • the high density polyethylene may exhibit a bimodal molecular weight distribution.
  • a bimodal distribution generally refers to a polymer having a distinct higher molecular weight and a distinct lower molecular weight (e.g. two distinct peaks) on a size exclusion chromatography or gel permeation chromatography curve.
  • the high density polyethylene may exhibit more than two molecular weight distribution peaks such that the polyethylene exhibits a multimodal (e.g., trimodal, tetramodal, etc.) distribution.
  • the high density polyethylene may exhibit a broad molecular weight distribution wherein the polyethylene is comprised of a blend of higher and lower molecular weight components such that the size exclusion chromatography or gel permeation chromatography curve does not exhibit at least two distinct peaks but instead exhibits one distinct peak broader than the individual component peaks.
  • the polyethylene powder is typically produced by the catalytic polymerization of ethylene monomer or optionally with one or more other 1 -olefin co-monomers, the 1 -olefin content in the final polymer being less or equal to 10% of the ethylene content, with a heterogeneous catalyst and an organo aluminum or magnesium compound as cocatalyst.
  • the ethylene is usually polymerized in gaseous phase or slurry phase at relatively low temperatures and pressures.
  • the polymerization reaction may be carried out at a temperature of between 50°C. and 100°C. and pressures in the range of 0.02 and 2 MPa.
  • the molecular weight of the polyethylene can be adjusted by adding hydrogen. Altering the temperature and/or the type and concentration of the co catalyst may also be used to fine tune the molecular weight. Additionally, the reaction may occur in the presence of antistatic agents to avoid fouling and product contamination.
  • Suitable catalyst systems include but are not limited to Ziegler-Natta type catalysts.
  • Ziegler-Natta type catalysts are derived by a combination of transition metal compounds of Groups 4 to 8 of the Periodic Table and alkyl or hydride derivatives of metals from Groups 1 to 3 of the Periodic Table. Transition metal derivatives used usually comprise the metal halides or esters or combinations thereof.
  • Exemplary Ziegler-Natta catalysts include those based on the reaction products of organo aluminum or magnesium compounds, such as for example but not limited to aluminum or magnesium alkyls and titanium, vanadium or chromium halides or esters.
  • the heterogeneous catalyst might be either unsupported or supported on porous fine grained materials, such as silica or magnesium chloride.
  • a suitable catalyst system can be obtained by the reaction of a titanium(IV) compound with a trialkyl aluminum compound in an inert organic solvent at temperatures in the range of -40°C. to 100°C., preferably -20°C. to 50°C.
  • concentrations of the starting materials are in the range of 0.1 to 9 mol/L, preferably 0.2 to 5 mol/L, for the titanium(IV) compound and in the range of 0.01 to 1 mol/L, preferably 0.02 to 0.2 mol/L for the trialkyl aluminum compound.
  • the titanium component is added to the aluminum component over a period of 0.1 min to 60 min, preferably 1 min to 30 min, the molar ratio of titanium and aluminum in the final mixture being in the range of 1 :0.01 to 1 :4.
  • a suitable catalyst system is obtained by a one or two-step reaction of a titanium(IV) compound with a trialkyl aluminum compound in an inert organic solvent at temperatures in the range of -40°C. to 200°C., preferably -20°C. to 150°C.
  • the titanium(IV) compound is reacted with the trialkyl aluminum compound at temperatures in the range of -40°C. to 100°C., preferably -20°C. to 50°C. using a molar ratio of titanium to aluminum in the range of 1 :0.1 to 1 :0.8.
  • the concentrations of the starting materials are in the range of 0.1 to 9.1 mol/L, preferably 5 to 9.1 mol/L, for the titanium(IV) compound and in the range of 0.05 and 1 mol/L, preferably 0.1 to 0.9 mol/L for the trialkyl aluminum compound.
  • the titanium component is added to the aluminum compound over a period of 0.1 min to 800 min, preferably 30 min to 600 min.
  • the reaction product obtained in the first step is treated with a trialkyl aluminum compound at temperatures in the range of -10° C. to 150° C., preferably 10° C. to 130° C. using a molar ratio of titanium to aluminum in the range of 1 :0.01 to 1 :5.
  • a suitable catalyst system is obtained by a procedure wherein, in a first reaction stage, a magnesium alcoholate is reacted with a titanium chloride in an inert hydrocarbon at a temperature of 50° to 100°C.
  • reaction mixture formed is subjected to heat treatment for a period of about 10 to 100 hours at a temperature of 110° to 200°C. accompanied by evolution of alkyl chloride until no further alkyl chloride is evolved, and the solid is then freed from soluble reaction products by washing several times with a hydrocarbon.
  • catalysts supported on silica such as for example the commercially available catalyst system Sylopol 5917 can also be used.
  • the polymerization is normally carried out in suspension at low pressure and temperature in one or multiple steps, continuous or batch.
  • the polymerization temperature is typically in the range of 30°C. to 130°C., preferably is the range of 50°C. and 90°C. and the ethylene partial pressure is typically less than 10 MPa, preferably 0.05 and 5 MPa.
  • Trialkyl aluminums like for example but not limited to isoprenyl aluminum and triisobutyl aluminum, are used as co-catalyst such that the ratio of AI:Ti (co-catalyst versus catalyst) is in the range of 0.01 to 100:1 , more preferably is the range of 0.03 to 50:1.
  • the solvent is an inert organic solvent as typically used for Ziegler type polymerizations. Examples are butane, pentane, hexane, cyclohexene, octane, nonane, decane, their isomers and mixtures thereof.
  • the polymer molecular mass is controlled through feeding hydrogen.
  • the ratio of hydrogen partial pressure to ethylene partial pressure is in the range of 0 to 50, preferably the range of 0 to 10.
  • the polymer is isolated and dried in a fluidized bed drier under nitrogen.
  • the solvent may be removed through steam distillation in case of using high boiling solvents. Salts of long chain fatty acids may be added as a stabilizer. Typical examples are calcium, magnesium and zinc stearate.
  • the high density polyethylene polymer is formed into particles and combined with a plasticizer.
  • the polyethylene particles are made from a polyethylene polymer having a relatively low bulk density as measured according to DIN53466.
  • the bulk density is generally less than about 0.4 g/cm 3 , such as less than about 0.35 g/cm 3 , such as less than about 0.33 g/cm 3 , such as less than about 0.3 g/cm 3 , such as less than about 0.28 g/cm 3 , such as less than about 0.26 g/cm 3 .
  • the bulk density is generally greater than about 0.1 g/cm 3 , such as greater than about 0.15 g/cm 3 .
  • the polymer has a bulk density of from about 0.2 g/cm 3 to about 0.27 g/cm 3 .
  • the polyethylene particles can be a free-flowing powder.
  • the particles can have a median particle size (d50) by volume of less than 200 microns.
  • the median particle size (d50) of the polyethylene particles can be less than about 150 microns, such as less than about 125 microns.
  • the median particle size (d50) is generally greater than about 20 microns.
  • the powder particle size can be measured utilizing a laser diffraction method according to ISO 13320.
  • 90% of the polyethylene particles can have a particle size of less than about 250 microns. In other embodiments, 90% of the polyethylene particles can have a particle size of less than about 200 microns, such as less than about 170 microns.
  • the molecular weight of the polyethylene polymer can vary depending upon the particular application.
  • the polyethylene polymer for instance, may have an average molecular weight, as determined according to the Margolies equation.
  • the molecular weight can be determined by first measuring the viscosity number according to DIN EN ISO Test 1628. Dry powder flow is measured using a 25 mm nozzle. The molecular weight is then calculated using the Margolies equation from the viscosity numbers.
  • the average molecular weight is generally greater than about 300,000 g/mol, such as greater than about 500,000 g/mol, such as greater than about 700,000 g/mol, such as greater than about 1 ,000,000 g/mol, such as greater than about 2,000,000 g/mol, such as greater than about 2,500,000 g/mol, such as greater than about 3,000,000 g/mol, such as greater than about 4,000,000 g/mol.
  • the average molecular weight is generally less than about 12,000,000 g/mol, such as less than about 10,000,000 g/mol.
  • the number average molecular weight of the high density polyethylene polymer can be less than about 4,000,000 g/mol, such as less than about 3,000,000 g/mol.
  • the polyethylene may have a viscosity number of from at least 100 mL/g, such as at least 500 mL/g, such as at least 1 ,500 mL/g, such as at least 2,000 mL/g, such as at least 4,000 mL/g to less than about 6,000 mL/g, such as less than about 5,000 mL/g, such as less than about 4000 mL/g, such as less than about 3,000 mL/g, such as less than about 1 ,000 mL/g, as determined according to ISO 1628 part 3 utilizing a concentration in decahydronapthalene of 0.0002 g/mL.
  • the high density polyethylene may have a crystallinity of from at least about 40% to 85%, such as from 45% to 80%.
  • the high density polyethylene particles are present in the polymer composition in an amount up to about 50% by weight.
  • the high density polyethylene particles can be present in the polymer composition in an amount less than about 45% by weight, such as in an amount less than about 40% by weight, such as in an amount less than about 35% by weight, such as in an amount less than about 30% by weight, such as in an amount less than about 25% by weight, such as in an amount less than about 20% by weight, such as in an amount less than about 15% by weight.
  • the polyethylene particles can be present in the composition in an amount greater than about 5% by weight, such as in an amount greater than about 10% by weight, such as in an amount greater than about 15% by weight, such as in an amount greater than about 20% by weight, such as in an amount greater than about 25% by weight.
  • a plasticizer is combined with the high density polyethylene particles which can be substantially or completely removed in forming polymer articles.
  • the resulting polymer article can contain the high density polyethylene polymer in an amount greater than about 70% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 85% by weight, such as in an amount greater than about 90% by weight, such as in an amount greater than about 95% by weight.
  • the polymer composition for producing gel extruded articles contains a shutdown reducing additive in combination with the high density polyethylene particles.
  • the shutdown reducing additive can also be present in the form of particles that are mixed or blended with the high density polyethylene particles. Melt blending the high density polyethylene particles with the shutdown reducing additive, for instance, may produce adverse consequences such as polymer entanglements that can make it difficult to produce gel extruded articles from the polymer composition.
  • the shutdown reducing additive is combined with the high density polyethylene particles in a manner that reduces the shutdown temperature of the polymer composition when formed into an article, such as a porous membrane.
  • the particular shutdown reducing additive selected for an application can depend upon various factors including the type of high density polyethylene particles that are combined with the shutdown reducing additive.
  • the shutdown reducing additive may comprise high density polyethylene particles that are different than the matrix polymer, low density polyethylene particles, linear low density polyethylene particles, metallocene linear low density polyethylene particles having a molecular weight distribution or polydispersity index of less than about 3, such as less than about 2.5, polyethylene wax particles, hydrogenated fatty acid particles, particles made from dimers of fatty acids, plastomer particles, elastomer particles, and mixtures thereof.
  • the shutdown reducing additive can be made from a polyethylene polymer.
  • the polyethylene polymer can be a high density polyethylene polymer, that has a molecular weight that is less than the molecular weight of the high density polyethylene matrix polymer.
  • the high density polyethylene polymer can have an average molecular weight of less than about 700,000 g/mol, such as less than about 500,000 g/mol, such as less than about 300,000 g/mol, such as less than about 100,000 g/mol.
  • the average molecular weight of the high density polyethylene polymer is generally greater than about 80,000 g/mol.
  • the shutdown reducing additive can be a middle density polyethylene.
  • a middle density polyethylene for instance, can have a density generally of from about 0.92 g/cm 3 to about 0.94 g/cm 3 .
  • the shutdown reducing additive can be a low density polyethylene.
  • Low density polyethylene can have a branched structure, which differentiates the polymer from a high density polyethylene or a linear low density polyethylene.
  • the polymer branching increases clarity, increases flexibility, and makes the polymer easy to melt process.
  • the molecular weight, crystallinity and molecular weight distribution of low density polyethylene can be varied depending upon the particular application.
  • the degree of crystallinity of low density polyethylene can be a function of the amount of branching present on the polymer molecules.
  • the crystallinity of the polymer for instance, can generally be greater than about 20%, such as greater than about 30%, and generally less than about 50%, such as less than about 40%.
  • the degree of crystallinity of low density polyethylene is generally less than the crystallinity of high density polyethylene, which can have crystallinity values of from about 50% to about 75%.
  • the low density polyethylene can generally have a narrow molecular distribution or a medium molecular weight distribution.
  • the molecular weight distribution can be from about 3 to about 5.
  • the molecular weight distribution can be from about 6 to about 12.
  • Molecular weight distribution is defined as the ratio of the weight average molecular weight to the number average molecular weight.
  • the shutdown reducing additive can also be a linear low density polyethylene.
  • Linear low density polyethylene polymer chains generally have no long chain branching.
  • the polymer can be produced at lower temperatures than low density polyethylene.
  • the linear low density polyethylene can be a polyethylene homopolymer or can be a copolymer of ethylene and higher alpha olefins, such as butene, hexene, or octene.
  • the linear low density polyethylene can have a density of greater than about 0.9 g/cm 3 , such as greater than about 0.91 g/cm 3 , and generally less than about 0.93 g/cm 3 , such as less than about 0.925 g/cm 3 .
  • the shutdown reducing additive can be a metallocene linear low density polyethylene.
  • Metallocene linear low density polyethylene is typically tougher than linear low density polyethylene and can have a density of between about 0.915 g/cm 3 and about 0.94 g/cm 3 .
  • the polymer is made using a metallocene catalyst.
  • Metallocene linear low density polyethylene can be a copolymer of ethylene with butene or hexene.
  • the metallocene linear low density polyethylene can have a molecular weight distribution or a polydispersity index of less than about 3.5, such as less than about 3, such as less than about 2.5.
  • the shutdown reducing additive can also be comprised of polyethylene wax particles.
  • a polyethylene wax generally has a vary low molecular weight. For instance, the average molecular weight can be less than about 12,000 g/mol, such as less than about 8,000 g/mol, such as less than about 6,000 g/mol, such as less than about 4,000 g/mol, such as less than about 2,000 g/mol. The number average molecular weight is generally greater than about 200 g/mol, such as greater than about 400 g/mol.
  • Polyethylene waxes are typically polyethylene homopolymers although copolymers exist as well. Polyethylene wax can either be formed from a low density polyethylene or a high density polyethylene. In one aspect, the polyethylene wax can have a molecular weight distribution of from about 1.5 to 5, such as from about 1 .5 to about 2.5.
  • the polymer can have a melt flow rate of generally from about 0.05 g/10 min to about 100 g/10 min (when measured at a load of 2.16 kg).
  • the melt flow rate can be greater than about 0.1 g/10 min, such as greater than about 0.8 g/10 min, such as greater than about 1 g/10 min, such as greater than about 1.5 g/10 min, such as greater than about 3 g/10 min, such as greater than about 5 g/10 min, such as greater than about 10 g/10 min, such as greater than about 20 g/10 min.
  • the melt flow rate is generally less than about 70 g/10 min, such as less than about 50 g/10 min, such as less than about 30 g/10 min, such as less than about 20 g/10 min.
  • the melt flow rate in one aspect, can be relatively low and can be less than about 10 g/10 min, such as less than about 8 g/10 min, such as less than about 6 g/10 min, such as less than about 4 g/10 min, such as less than about 3 g/10 min, such as less than about 2 g/10 min.
  • the polyethylene polymer can be in the form of particles.
  • the particles can have an average d50 particle size of generally greater than about 100 microns, such as greater than about 200 microns, such as greater than about 250 microns, such as greater than about 300 microns, and generally less than about 1 ,000 microns, such as less than about 900 microns, such as less than about 800 microns, such as less than about 600 microns, such as less than about 500 microns.
  • the density of the polyethylene polymer can generally be anywhere from about 0.91 g/cm 3 to about 0.95 g/cm 3 including all increments of 0.01 g/cm 3 therebetween.
  • the shutdown reducing additive can also comprise a fatty acid derivative, such as a hydrogenated fatty acid or a dimer of a fatty acid.
  • Hydrogenated fatty acids are fatty acids where the majority of double bonds have been converted to single bonds.
  • the hydrogenated fatty acid can be formed from a fatty acid having a carbon chain length of greater than about 12 carbon atoms, such as greater than about 16 carbon atoms, such as greater than about 18 carbon atoms, such as greater than about 20 carbon atoms, such as greater than about 24 carbon atoms, and generally less than about 52 carbon atoms, such as less than about 48 carbon atoms, such as less than about 38 carbon atoms.
  • Dimers of fatty acids or dimerized fatty acids are prepared by dimerizing unsaturated fatty acids obtained from tall oil.
  • a dimerized fatty acid can be formed from a fatty acid having a carbon chain length as described above with respect to hydrogenated fatty acids.
  • the shutdown reducing additive can comprise elastomer particles.
  • Thermoplastic elastomers include styrenic block copolymers, olefin elastomers, polyester elastomers, polyamide elastomers, and polyurethane elastomers.
  • Styrenic block copolymers include styrene-ethylene- ethylene-propylene-styrene polymers, styrene-ethylene-butylene-styrene polymers, and styrene-butadiene-styrene polymers.
  • the elastomer particles are made from a polyurethane elastomer.
  • the thermoplastic polyurethane elastomer may have a soft segment of a long-chain diol and a hard segment derived from a diisocyanate and a chain extender.
  • the polyurethane elastomer is a polyester type prepared by reacting a long-chain diol with a diisocyanate to produce a polyurethane prepolymer having isocyanate end groups, followed by chain extension of the prepolymer with a diol chain extender.
  • polyester diols such as polybutylene adipate)diol, polyethylene adipate)diol and poly(£-caprolactone)diol
  • polyether diols such as poly(tetramethylene ether)glycol, polypropylene oxide)glycol and polyethylene oxide)glycol.
  • Suitable diisocyanates include 4,4'-methylenebis(phenyl isocyanate), 2,4-toluene diisocyanate, 1 ,6-hexamethylene diisocyanate and 4,4'-methylenebis- (cycloxylisocyanate).
  • Suitable chain extenders are C2-C6 aliphatic diols such as ethylene glycol, 1 ,4-butanediol, 1 ,6-hexanediol and neopentyl glycol.
  • a thermoplastic polyurethane is characterized as essentially poly(adipic acid-co- butylene glycol-co-diphenylmethane diisocyanate).
  • the elastomer particles can also be made from a copolyester elastomer.
  • the copolyester elastomer can include ester and ether bonds.
  • the copolyester elastomer can have an alternating structure defined by a multiplicity of randomly recurring long-chain ester units and short-chain ester units, joined together by head-to-tail chaining through ester bonds.
  • - G is a divalent group that remains after removal of terminal hydroxyl groups from a polyol having a molecular weight between about 250 and 6000;
  • - R is a divalent group that remains after removal of carboxyl groups from a dicarboxylic acid having a molecular weight less than about 300;
  • - D is a divalent group remaining after removal of hydroxyl groups from a diol having a molecular weight less than about 250.
  • the expression “divalent group” means a group having two hydroxyl reactive centres positioned one at the head and one at the tail to the molecule.
  • the expression “divalent group” means a group having two carboxyl reactive centres positioned one at the head and one in the tail to the molecule.
  • the R groups are the groups that provide the polyester bond.
  • the R groups have an aromatic part, they confer crystallinity to the copolyester.
  • the G groups in combination with the R groups confer the elastomer properties to the copolyester.
  • the D groups in combination with the R groups confer properties of rigidity to the copolyester.
  • the above alternating structure can comprise from 5% to 15% by weight of short-chain ester units and from 70% to 80% by weight of long-chain ester units.
  • the alternating structure thermoplastic copolyester elastomer can be obtained according to the following general reaction scheme:
  • the molecular weight of the copolyester elastomer can vary depending upon the particular application. In one embodiment, for instance, the molecular weight of the copolyester elastomer is greater than about 20,000 g/mol, such as greater than about 25,000 g/mol, such as greater than about 28,000 g/mol, such as greater than about 30,000 g/mol, such as greater than about 35,000 g/mol, such as greater than about 40,000 g/mol, such as greater than about 45,000 g/mol, such as greater than about 50,000 g/mol.
  • the molecular weight of the polyester elastomer is generally less than about 200,000 g/mol, such as less than about 100,000 g/mol.
  • the shutdown reducing additive can be a plastomer.
  • a plastomer is a polymer material which combines the qualities of elastomers and thermoplastics.
  • a polyolefin plastomer is used that comprises an alpha olefin copolymer, particularly an alpha olefin polyethylene copolymer. Suitable alpha-olefins may be linear or branched (e.g., one or more C1-C3 alkyl branches, or an aryl group).
  • Specific examples include ethylene, 1- butene; 3-methyl-1 -butene; 3, 3-dimethyl-1 -butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1 -hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1- nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1-decene; 1-dodecene; and styrene.
  • alpha-olefin comonomers are ethylene, 1 -butene, 1 -hexene and 1-octene.
  • the ethylene content of such copolymers may be from about 60 mole % to about 99.5 wt. %, in some embodiments from about 80 mole % to about 99 mole %, and in some embodiments, from about 85 mole % to about 98 mole %.
  • the alpha-olefin content may likewise range from about 0.5 mole % to about 40 mole %, in some embodiments from about 1 mole % to about 20 mole %, and in some embodiments, from about 2 mole % to about 15 mole %.
  • the distribution of the alpha-olefin comonomer is typically random and uniform among the differing molecular weight fractions forming the ethylene copolymer.
  • the density of the plastomer may generally be less than about 0.95 g/cc, such as less than about 0.91 g/cc.
  • the density of the polyolefin is generally greater than about 0.8 g/cc, such as greater than about 0.85 g/cc, such as greater than about 0.88 g/cc.
  • the plastomer can have a glass transition temperature of less than about 35°C, such as less than about 25°C.
  • the shutdown reducing additive is in the form of particles that are combined with the high density polyethylene particles.
  • the shutdown reducing additive particles have a median particle size by volume of less than about 800 microns, such as less than about 600 microns, such as less than about 400 microns, such as less than about 200 microns.
  • the median particle size of the shutdown reducing additive is generally greater than about 10 microns, such as greater than about 20 microns, such as greater than about 50 microns, such as greater than about 70 microns.
  • the shutdown reducing additive particles can be selected, ground or milled so that the particle size substantially matches the particle size of the high density polyethylene particles.
  • the median particle size of the shutdown reducing additive can be within about 20% (+ or -) such as within about 10% of the median particle size of the high density polyethylene particle.
  • the shutdown reducing additive generally has a melt flow rate of from about 0.01 g/10 mins to about 110 g/10 mins, such as from about 0.03 g/10 mins to about 70 g/10 mins, such as from about 0.05 g/10 min to about 50 g/10 min.
  • melt flow rate can be measured using ISO Test 1133 at a temperature of 190°C and at a load of 2.16 kg. More particularly, the melt flow rate of the shut reducing additive can be greater than about 2 g/10 min, such as greater than about 7 g/10 min, such as greater than about 10 g/ 10 min, and generally less than about 60 g/10 min, such as less than about 40 g/10min, such as less than about 30 g/10 min, such as less than about 25 g/10 min, such as less than about 20 g/10 min.
  • the shutdown reducing additive (any of the shutdown reducing additives identified above) can have a melting point of generally less than about 130°C, such as less than about 129°C, such as less than about 128°C.
  • the melting point is generally greater than about 105°C, such as greater than about 115°C.
  • the shutdown reducing additive is generally present in the polymer composition in conjunction with the high density polyethylene particles and the plasticizer in an amount from 2% by weight to about 40% by weight.
  • the shutdown reducing additive can be present in the polymer composition in an amount greater than about 2% by weight, such as in an amount greater than about 4% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, such as in an amount greater than about 12% by weight, such as in an amount greater than about 15% by weight, such as in an amount greater than about 18% by weight, such as in an amount greater than about 20% by weight, such as in an amount greater than about 22% by weight, and generally less than about than 40% by weight, such as in an amount less than about 35% by weight, such as in an amount less than about 30% by weight, such an in an amount less than about 20% by weight, such as in an amount less than about 15% by weight.
  • the shutdown reducing additive can be present in the final product, such as a porous membrane, in an amount greater than about 3% by weight, such as in an amount greater than about 5% by weight, such as in an amount greater than about 7% by weight, such as in an amount greater than about 8% by weight, such as in an amount greater than about 10% by weight, such as in an amount greater than about 12% by weight, and generally less than about 30% by weight, such as in an amount less than about 25% by weight, such as in an amount less than about 20% by weight, such as in an amount less than about 15% by weight, such as in an amount less than about 10% by weight.
  • the effect the shutdown reducing additive has on the shutdown temperature of polymer articles made from the polymer composition can depend upon various factors.
  • one or more shutdown reducing additives are incorporated into the polymer composition such that the shutdown temperature of the polymer composition is reduced by at least 1 8°C, such as at least 2.2°C, such as at least 2.5°C, such as at least 2.8°C, such as at least 3°C, such as at least 3.3°C, such as at least 3.5°C, such as at least 3.8°C, such as at least 4°C in comparison to articles made from the polymer composition where the shutdown reducing additive is replaced by further amounts of the high density polyethylene particles.
  • the shutdown temperature of the polymer composition is reduced by at least 5°C, such as at least 6°C, such as at least 7°C.
  • the amount the shutdown temperature is reduced through use of the additive is somewhat more important than the final or ultimate shutdown temperature of the polymer composition.
  • the additive of the present disclosure allows for the use of polyethylene polymers having higher shutdown temperatures and greater performance.
  • the additive of the present disclosure for instance, can be combined with these polymers for keeping the shutdown temperature within levels used in the past through the use of polyethylene polymers having inferior properties.
  • the shutdown temperature of articles made from the polymer composition can be at a temperature of 133.7°C or less, such as 133.4°C or less, such as 132.9°C or less, such as 132.5°C or less, such as 132.3°C or less, such as 132°C or less, such as 131 7°C or less, such as 131 5°C or less, such as 131 3°C or less, such as 131 °C or less.
  • the shutdown temperature for instance, can be 130°C or less, such as 129°C or less.
  • the shutdown temperature is generally greater than about 120°C, such as greater than about 125°C.
  • the above shutdown temperatures are based upon measurements of the polymer article using the Impedance Test.
  • the polymer composition further contains a plasticizer.
  • a plasticizer can be combined with the other components as long as the plasticizer is capable of forming a gel-like material suitable for gel spinning or extruding.
  • the plasticizer may comprise a hydrocarbon oil, an alcohol, an ether, an ester such as a diester, or mixtures thereof.
  • suitable plasticizers include mineral oil, a paraffinic oil, decaline, and the like.
  • plasticizers include xylene, dioctyl phthalate, dibutyl phthalate, stearyl alcohol, oleyl alcohol, decyl alcohol, nonyl alcohol, diphenyl ether, n-decane, n- dodecane, octane, nonane, kerosene, toluene, naphthalene, tetraline, and the like.
  • the plasticizer may comprise a halogenated hydrocarbon, such as monochlorobenzene.
  • Cycloalkanes and cycloalkenes may also be used, such as camphene, methane, dipentene, methylcyclopentandiene, tricyclodecane, 1 ,2,4,5-tetramethyl-1 ,4-cyclohexadiene, and the like.
  • the plasticizer may comprise mixtures and combinations of any of the above as well.
  • the plasticizer is generally present in the composition used to form the polymer articles in an amount greater than about 50% by weight, such as in an amount greater than about 55% by weight, such as in an amount greater than about 60% by weight, such as in an amount greater than about 65% by weight, such as in an amount greater than about 70% by weight, such as in an amount greater than about 75% by weight, such as in an amount greater than about 80% by weight, such as in an amount greater than about 85% by weight, such as in an amount greater than about 90% by weight, such as in an amount greater than about 95% by weight, such as in an amount greater than about 98% by weight.
  • the plasticizer can be present in an amount up to about 99.5% by weight.
  • the high density polyethylene particles are combined with the shutdown reducing additive and the plasticizer and extruded through a die of a desired shape.
  • the composition can be heated within the extruder.
  • the plasticizer can be combined with the particle mixture and fed into an extruder.
  • the plasticizer and particle mixture form a homogeneous gel-like material prior to leaving the extruder for forming polymer articles with little to no impurities.
  • elongated articles are formed during the gel spinning or extruding process.
  • the polymer article for instance, may be in the form of a fiber or a film, such as a membrane.
  • the plasticizer removal process may occur due to evaporation when a relatively volatile plasticizer is used. Otherwise, an extraction liquid can be used to remove the plasticizer.
  • the extraction liquid may comprise, for instance, a hydrocarbon solvent.
  • One example of the extraction liquid, for instance, is dichloromethane.
  • Other extraction liquids include acetone, chloroform, an alkane, hexene, heptene, an alcohol, or mixtures thereof.
  • the resulting polymer article can be stretched at an elevated temperature below the melting point of the polymer mixture to increase strength and modulus. Suitable temperatures for stretching are in the range of from about ambient temperature to about 155°C.
  • the draw ratios can generally be greater than about 4, such as greater than about 6, such as greater than about 8, such as greater than about 10, such as greater than about 15, such as greater than about 20, such as greater than about 25, such as greater than about 30.
  • the draw ratio can be greater than about 50, such as greater than about 100, such as greater than about 110, such as greater than about 120, such as greater than about 130, such as greater than about 140, such as greater than about 150.
  • Draw ratios are generally less than about 1 ,000, such as less than about 800, such as less than about 600, such as less than about 400. In one embodiment, lower draw ratios are used such as from about 4 to about 10.
  • the polymer article can be uniaxially stretched or biaxially stretched.
  • the process is used to produce a membrane.
  • the membrane can be used, for instance, as a battery separator.
  • the membrane can be used as a microfilter.
  • the fibers can be used to produce nonwoven fabrics, ropes, nets, and the like.
  • the fibers can be used as a filler material in ballistic apparel.
  • the battery 10 includes an anode 12 and a cathode 14.
  • the anode 12 for instance, can be made from a lithium metal.
  • the battery 10 further includes a porous membrane 16 or separator that is positioned inbetween the anode 12 and the cathode 14. The porous membrane 16 minimizes electrical shorts between the two electrodes while allowing the passage of ions, such as lithium ions. As shown in Fig.
  • the porous membrane 16 is a single layer polymer membrane and does not include a multilayer structure.
  • the single layer polymer membrane may also include a coating.
  • the coating can be an inorganic coating made from, for instance, aluminum oxide or a titanium oxide.
  • the single layer polymer membrane may also include a polymeric coating. The coating can provide increased thermal resistance.
  • the polymer composition and polymer articles made in accordance with the present disclosure may contain various other additives, such as heat stabilizers, light stabilizers, UV absorbers, acid scavengers, flame retardants, lubricants, colorants, and the like.
  • a heat stabilizer may be present in the composition.
  • the heat stabilizer may include, but is not limited to, phosphites, aminic antioxidants, phenolic antioxidants, or any combination thereof.
  • an antioxidant may be present in the composition.
  • the antioxidant may include, but is not limited to, secondary aromatic amines, benzofuranones, sterically hindered phenols, or any combination thereof.
  • a light stabilizer may be present in the composition.
  • the light stabilizer may include, but is not limited to, 2-(2'-hydroxyphenyl)- benzotriazoles, 2-hydroxy-4-alkoxybenzophenones, nickel containing light stabilizers, 3,5-di-tert-butyl-4-hydroxbenzoates, sterically hindered amines (HALS), or any combination thereof.
  • a UV absorber may be present in the composition in lieu of or in addition to the light stabilizer.
  • the UV absorber may include, but is not limited to, a benzotriazole, a benzoate, or a combination thereof, or any combination thereof.
  • a halogenated flame retardant may be present in the composition.
  • the halogenated flame retardant may include, but is not limited to, tetrabromobisphenol A (TBBA), tetrabromophthalic acid anhydride, dedecachloropentacyclooctadecadiene (dechlorane), hexabromocyclodedecane, chlorinated paraffins, or any combination thereof.
  • a non-halogenated flame retardant may be present in the composition.
  • the non-halogenated flame retardant may include, but is not limited to, resorcinol diphosphoric acid tetraphenyl ester (RDP), ammonium polyphosphate (APP), phosphine acid derivatives, triaryl phosphates, trichloropropylphosphate (TCPP), magnesium hydroxide, aluminum trihydroxide, antimony trioxide.
  • a lubricant may be present in the composition.
  • the lubricant may include, but is not limited to, silicone oil, waxes, molybdenum disulfide, or any combination thereof.
  • a colorant may be present in the composition.
  • the colorant may include, but is not limited to, inorganic and organic based color pigments.
  • an acid scavenger may be present in the polymer composition.
  • the acid scavenger may comprise an alkali metal salt or an alkaline earth metal salt.
  • the salt can comprise a salt of a fatty acid, such as a stearate.
  • Other acid scavengers include carbonates, oxides, or hydroxides.
  • Particular acid scavengers that may be incorporated into the polymer composition include a metal stearate, such as calcium stearate.
  • Still other acid scavengers include zinc oxide, calcium carbonate, magnesium oxide, and mixtures thereof.
  • each additive may be present in the polymer composition or in the resulting polymer article in an amount of at least about 0.05 wt. %, such as in an amount of at least about 0.1 wt. %, such as at least about 0.25 wt. %, such as at least about 0.5 wt. %, such as at least about 1 wt. % and generally less than about 20 wt. %, such as less than about 10 wt. %, such as less than about 5 wt. %, such as less than about 4 wt. %, such as less than about 2 wt. %.
  • the sum of the wt. % of all of the components, including any additives if present, utilized in the polymer composition and articles will be 100 wt. %.
  • the shutdown reducing additives used were low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).
  • the shutdown reducing additive was a plastomer.
  • the plastomer was an alpha-olefin random copolymer. More specifically, the plastomer used was an octene-ethylene random copolymer.
  • Shutdown temperatures of the modified compositions containing additives were compared with the shutdown temperatures of unmodified resins in which no additives were used. The shutdown temperatures of the resulting membranes were determined using three independent methods: directly by impedance spectroscopy, indirectly via softening point by dynamic thermomechanical analysis (TMA), and indirectly via melting point by differential scanning calorimetry (DSC).
  • TMA dynamic thermomechanical analysis
  • DSC differential scanning calorimetry
  • Fig. 1 is a graphical representation of the Impedance Test carried out on Example No. 1 and Example No. 3. As shown, Example No. 3 containing the linear low density polyethylene dramatically decreased the shutdown temperature. The shutdown temperature was decreased without effecting other properties of the porous membrane.
  • Example 1 The procedures of Example 1 were repeated using various different shut down reducing additives in different amounts. All of the shutdown reducing additives were polyethylene polymers such as linear low density polyethylene polymers, high density polyethylene polymers, and low density polyethylene polymers. More particularly, the different samples included the following shut down reducing additives:
  • Sample Nos. 38 and 39 Combination of Sample No. 22 and Sample No. 28 in a 50:50 weight ratio.
  • Sample Nos. 40 and 41 Combination of Sample No. 30 and Sample No. 34 in a 50:50 weight ratio.

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  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)

Abstract

L'invention concerne une composition de polymère destinée à produire des articles extrudés en gel. La composition de polymère contient des particules de polyéthylène combinées à un plastifiant et à un ou plusieurs additifs réducteurs d'arrêt. Les additifs réducteurs d'arrêt diminuent la température d'arrêt des articles en polymère fabriqués à partir de la composition polymère. Dans un mode de réalisation, la composition polymère est utilisée pour former une membrane poreuse destinée à être utilisée dans un séparateur.
PCT/US2021/030095 2020-05-01 2021-04-30 Membrane à température d'arrêt réduite et composition polymère pour sa fabrication WO2021222709A1 (fr)

Priority Applications (6)

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EP21797222.3A EP4143139A4 (fr) 2020-05-01 2021-04-30 Membrane à température d'arrêt réduite et composition polymère pour sa fabrication
CN202180047330.4A CN115803291A (zh) 2020-05-01 2021-04-30 具有降低的关闭温度的膜和用于制造其的聚合物组合物
JP2022566638A JP2023524104A (ja) 2020-05-01 2021-04-30 低下したシャットダウン温度を有する膜および同膜を作製するためのポリマー組成物
MX2022013577A MX2022013577A (es) 2020-05-01 2021-04-30 Membrana que tiene una temperatura de apagado reducida y composición de polímeros para la fabricación de la misma.
BR112022022254A BR112022022254A2 (pt) 2020-05-01 2021-04-30 Membrana que tem uma temperatura de desativação reduzida e composição de polímero para fazer a mesma
KR1020227042121A KR20230005958A (ko) 2020-05-01 2021-04-30 셧다운 온도가 감소된 막 및 이의 제조를 위한 중합체 조성물

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CN115803291A (zh) 2023-03-14
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JP2023524104A (ja) 2023-06-08
KR20230005958A (ko) 2023-01-10

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